This invention relates to a warming composition which produces an excellent warming effect of long duration with no or little skin irritation, a fragrant composition comprising the warming composition, and cosmetics, toiletries, bath additives, and pharmaceuticals containing the warming composition or the fragrance composition.
Substances which are known to provide a sensation of warmth on application and called xe2x80x9cwarming agentsxe2x80x9d include polyhydric alcohols, capsicum (red pepper) powder, a capsicum tincture, capsicum extract, capsaicin, homocapsaicin, homodihydrocapsaicin, nonanoyl vanillyl amide, nonanoic acid vanillyl ether, vanillyl alcohol alkyl ether derivatives (JP-A-57-9729), such as vanillyl ethyl ether, vanillyl butyl ether, vanillyl pentyl ether, and vanillyl hexyl ether, isovanillyl alcohol alkyl ethers, ethylvanillyl alcohol alkyl ethers, veratryl alcohol derivatives, substituted benzyl alcohol derivatives, substituted benzyl alcohol alkyl ethers, vanillin propylene glycol acetal, ethylvanillin propylene glycol acetal, ginger extract, ginger oil, gingeol, and gingeron.
These warming agents are added either as such or in the form of a fragrance composition to various products to produce a warming effect. However, the known warming agents often cause strong skin irritation or exhibit insufficient warming effects, and those having high warming effects are of short duration or, when used in a reduced amount, have insufficient warming effects or an insufficient duration of effect.
An object of the present invention is to provide a warming composition which is freed of these problems, i.e., causes no or little skin irritation and exhibits an excellent and long-lasting warming effect in a small amount.
Another object of the present invention is to provide a fragrance composition which causes no or little skin irritation and imparts a long-lasting warming effect when added in a small amount.
Still another object of the invention is to provide cosmetics, toiletries, bath additives and pharmaceuticals which contain the warming composition or the fragrance composition and exhibit excellent and long-lasting warming effects.
As a result of extensive investigations, the inventors have found that a combination of (A) a compound or a composition that has been known as a cooling agent (hereinafter inclusively referred to as a cooling agent) and a small amount of a compound represented by formula (I) (B) and/or (C) a compound or a composition that has been known as a warming agent (hereinafter inclusively referred to as a warming agent) produces such a warming effect as is never expected from each of the components used alone and as lasts as long as 3 hours or even more, and, when added to a product, exhibits an appreciable warming effect in such a low concentration at which each component would not stimulate individually, making it possible to produce a warming effect with no skin irritation that has not heretofore been attained.
The present invention provides a warming composition comprising (A) a cooling agent and (B) a compound represented by formula (I): 
wherein R1 represents a hydrogen atom, a methyl group or an ethyl group.
The present invention provides a warming composition comprising (A) a cooling agent and (C) a warming agent.
The present invention provides a warming composition comprising (A) a cooling agent, (B) a compound represented by formula (I), and (C) a warming agent.
The present invention also provides a fragrance composition comprising any of the above-described warming compositions.
The present invention also provides cosmetics, toiletries, bath additives or pharmaceuticals comprising any of the above-described warming compositions or the above-described fragrance composition.
In the present invention, a combination of a cooling agent and at least one of a warming agent and a specific compound produces an appreciable warming effect at such a low concentration at which each component alone is ineffective. The warming effect of the warming composition lasts for a long period of time that has not been thought. The warming composition is unlike conventional ones in that when it is applied to one""s sole, the warming effect is also produced in her or his back, etc.
The warming composition of the present invention comprises (A) a cooling agent and at least one of (B) a compound represented by formula (I) and (C) a warming agent.
The cooling agent as component (A) can be any compound or composition known as a cooling agent. Typical examples of the cooling agents which can be used in the present invention include:
(1) a compound represented by formula (II): 
wherein R2 and R3 each represent a hydrogen atom or a hydroxyl group (represents a single bond or a double bond, the same definition applies hereinafter),
(2) a compound represented by formula (III): 
wherein R4 represents a hydrogen atom or a methyl group; R5 represents a hydrogen atom, a lower alkyl group or a 2-alkoxyethyl group,
(3) a compound represented by formula (IV): 
wherein n represents an integer of 1 to 10,
(4) a compound represented by formula (V): 
wherein R6 represents a hydrogen atom, a straight-chain or branched alkyl or alkenyl group, or a straight-chain or branched hydroxyalkyl group,
(5) l-menthylacetic acid N-ethylamide, and (6) N,2,3-trimethyl-2-(1-methylethyl)-butanamide.
Specific examples of the cooling agents which are preferably used in the invention include, but are not limited to, menthol, isopulegol, 3-(l-menthoxy)propane-1,2-diol, 3-(l-menthoxy)-2-methylpropane-1,2-diol, p-menthane-2,3-diol, p-menthane-3,8-diol, 6-isopropyl-9-methyl-1,4-dioxaspiro[4,5]decane-2-methanol, menthyl succinate and its alkaline earth metal salts, trimethylcyclohexanol, N-ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, Japanese mint (Mentha arvensis) oil, peppermint oil, menthone, menthone glycerol ketal, menthyl lactate, 3-(l-menthoxy)ethan-1-ol, 3-(l-menthoxy)propan-1-ol, 3-(l-menthoxy)butan-1-ol, l-menthylacetic acid N-ethylamide, l-menthyl-4-hydroxypentanoate, l-menthyl-3-hydroxybutyrate, N,2,3-trimethyl-2-(1-methylethyl)-butanamide, and spearmint oil.
Of these cooling agents preferred are 3-(l-menthoxy)propane-1,2-diol, 3-(l-menthoxy)-2-methylpropane-1,2-diol, p-menthane-3,8-diol, 3-(l-menthoxy)ethan-1-ol, 3-(l-menthoxy)propan-1-ol, and 3-(l-menthoxy)butan-1-ol. Still preferred are 3-(l-menthoxy)propane-1,2-diol and 3-(l-menthoxy)-2-methylpropane-1,2-diol.
Of the compounds represented by formula (I) as component (B) the compound in which R1 is a methyl group, i.e., vanillin is preferred.
The warming agent as component (C) includes, but is not limited to,
(i) vanillyl alcohol, vanillyl alkyl or alkenyl ethers represented by formula (VI): 
wherein R7 represents a hydrogen atom or a straight chain or branched alkyl or alkenyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms,
such as vanillyl ethyl ether, vanillyl propyl ether, vanillyl butyl ether, vanillyl pentyl ether, and vanillyl hexyl ether;
(ii) vanillin propylene glycol acetal;
(iii) ethylvanillin propylene glycol acetal;
(iv) compounds represented by formula (VII): 
wherein R8 represents a straight-chain or branched alkyl or alkenyl group,
such as capsaicin and nonanoic acid vanillylamide;
(v) gingeron, capsicum tincture, and ginger extract.
Other substances that have been described as a warming agent in the background of the present invention can be used.
Of the above recited warming agents preferred are vanillyl ethyl ether, vanillyl propyl ether, vanillyl butyl ether, vanillyl pentyl ether, vanillyl hexyl ether, gingeron, capsicum tincture, and ginger extract. Still preferred are vanillyl butyl ether, vanillyl pentyl ether, vanillyl hexyl ether, and capsicum tincture. Vanillyl butyl ether is the most preferred.
Component (B) is usually used in an amount of 0.000001 to 100 parts, preferably 0.0001 to 10 parts, still preferably 0.001 to 1 part, by weight per part by weight of component (A), and component (C) is usually used in an amount of 0.5 to 100 parts, preferably 0.5 to 10 parts, still preferably 0.5 to 1 part, by weight per part by weight of component (A). Where the warming composition comprises both components (B) and (C), components (B) and (C) are used in an a total amount of 0.000001 to 100 parts, preferably 0.0001 to 10 parts, by weight per part by weight of component (A). The weight ratio of component (C) to component (B) is preferably 0.01 to 100.
A preferred combination of components (A), (B), and (C) includes a combination of (A) 3-(l-menthoxy)propane-1,2-diol or 3-(l-menthoxy)-2-methylpropane-1,2-diol and (B) vanillin and/or (C) vanillyl butyl ether. In this case, the combination usually comprises 0.0001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, of component (B) and 0.5 to 5 parts by weight of component (C) each per part by weight of component (A).
The warming composition, which comprises component (A) and components (B) and/or (C), may be diluted with a diluent safe to a human body, such as ethanol or pure water at an appropriate dilution decided according to the intended use, for example, about 1:2 to 1:10000.
The warming composition can be incorporated into a fragrance composition. The fragrance composition is not particularly limited, and any fragrance composition known in the art is used. Examples of suitable fragrance compositions include, as classified by note, those having a citrus note, a green note, a floral note, an aldehyde note, a fruity note, a woody note, a mossy note, a sweet note, a musky note, an amber note, an animal note, a minty note, a herbal note, and a marine note; and, as classified according to floral essential oils, blackcurrant, boronia broom, capucine, carnation, cassie, champaca, chrysanthemum, clover, cyclamen, freesia, gardenia, helichrysum, heliotrope, honeysuckle, hyacinth, jasmine, karo-karonde, lilac, lily, lily-of-the-valley, linden blossom, magnolia, marigold, mimosa, narcissus, neroli, orange flower, orchid, osmanthus, poppy, reseda, rose, stephanotis, sweet pea, tuberose, verbena, violet, wallflower, wisteria, ylang ylang, lavender, and jonquille. The warming composition of the invention can be used as a blending component or an additive component in blending synthetic or natural fragrance components or as an additive after blending.
The warming composition or the fragrance composition of the invention can be used as an additive component to various products. The content of the warming composition in a final product is subject to wide variation according to the kind of the product, the amount of the product to be applied, the mode of use or application of the product, and the like. In general, the content of each of components (A), (B), and (C) in a final product can range from 0.000001 to 10%, preferably 0.0001 to 1%, still preferably 0.001 to 0.5%, by weight based on the final product. Component (A) and components (B) and/or (C) may be added to a product either separately with or without an appropriate solvent or in the form of a composition previously prepared from the components (i.e., the warming composition or the fragrance composition). They may be added as compounding components in the course of producing the product.
The warming composition can be used in cosmetics, toiletries, bath additives, pharmaceuticals, etc. as a component for providing warmth or as a component for providing a sustained, long-lasting sensation of warmth. Cosmetics and toiletries to which the warming composition is added include, but are not limited to, soaps, body shampoos, shampoos, hair rinses, hair conditioners, hair treatments, antiperspirants, skin lotions, skin creams, moisturizers, deodorants, cologne, perfumes, lipsticks, lip creams, and so forth. The pharmaceuticals to which the warming composition is added include, but are not limited to, applications, such as poultices.
These products can contain various additives in addition to the warming composition of the invention, such as circulation stimulants, antiinflammatory agents, humectants, astringents, antibacterial and/or antifungal agents, inorganic salts, organic salts, oily components, surface active agents, crude drugs, pigments, perfumes, sulfur, sinter deposit, bactericides, and so forth.
The products containing the warming composition of the invention are described more specifically with particular reference to external application for skin, such as cosmetics, and bath additives.
External applications for skin, such as cosmetics, can contain the warming composition in an arbitrary amount, for example, 0.00001 to 10%, particularly 0.001 to 1%, by weight based on the total preparation.
The external application for skin of the present invention can further contain, in addition to the warming composition, powders commonly used in cosmetic formulations, such as inorganic powders and organic powders (e.g., homopolymers, copolymers, resins). Preferred of them are talc, sericite, mica, kaolin, silicone resin, and nylon for their good feel.
It is preferred for the powder to have an average particle size of 0.1 to 15 xcexcm, particularly 1 to 10 xcexcm. From the standpoint of feel on use, the powder is preferably added in an amount of 1 to 60% by weight, particularly 5 to 25% by weight, based on the external application for skin.
The external application for skin of the present invention can further contain oily substances. Oily substances that are preferred for feel on use include avocado oil, tsubaki oil, turtle oil, corn oil, olive oil, wheat embryo oil, soybean oil, jojoba oil, peanut oil, cacao butter, lanolin, liquid paraffin, squalane, squalene, vaseline, cholesteryl esters, and silicone oil.
Of these oily substances preferred for the feel on use are those having a surface tension of 30 dyn/cm or less at 25xc2x0 C., particularly silicone oil, such as methylpolysiloxane, dimethylpolysiloxane, methylcyclopolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, fatty acid-modified polysiloxane, higher alcohol-modified polysiloxane, and amino-modified polysiloxane. In particular, methylpolysiloxane and dimethylpolysiloxane are preferred. The most preferred are those having a viscosity of 200 centistokes (cs) or less at 25xc2x0 C. for their effects on improving the feel on use.
A preferred content of the oily substance in the external application for skin is 0.1 to 20%, particularly 1 to 10%, by weight. In order to secure retention of the powdery component on the skin, the oily substance and the powder are preferably used at a weight ratio of 1:20 to 20:1, particularly 1:1 to 1:10.
The external application for skin can contain alcohols. Preferable alcohols include ethyl alcohol, propylene glycol, 1,3-butylene glycol, glycerol, and sorbitol. The alcohols may be used either individually or as a combination of two or more. From the viewpoint of feel on use, the alcohols are preferably used in an amount of 0.1 to 30%, particularly 1 to 20%, by weight based on the composition.
The external application for skin can further contain physiologically effective humectants, antiinflammatory agents, skin whitening agents, ultraviolet absorbents, bactericides, antiperspirants, perfumes, and the like.
The external application for skin of the invention can have any conceivable form selected according to the site or occasion of application and include, for example, lotions, emulsions, creams, powders, poultices, packs, massaging preparations, gels, pastes, and sprays.
Where the warming composition is incorporated into bath additives, the amount to be added is preferably, but not limited to, 0.000001 to 1%, particularly 0.0001 to 0.1%, by weight based on the total bath additives.
The bath additives is put in bath water preferably in a concentration of 0.00015 to 150 ppm, particularly 0.015 to 15 ppm.
If desired, the bath additives can contain inorganic salts, organic acids, oily components, and the like in addition to the warming composition. The inorganic salts include sodium chloride, sodium hydrogencarbonate, sodium carbonate, borax, sodium sulfate, sodium sulfide, sodium sesquicarbonate, sodium nitrate, sodium thiosulfate, sodium polyphosphate, sodium phosphate, calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, potassium chloride, and potassium sulfide. Among them preferred are sodium chloride, sodium hydrogencarbonate, sodium carbonate, sodium sulfate, sodium sesquicarbonate, magnesium oxide, calcium carbonate, and magnesium carbonate. They can be used either individually or as a combination thereof. A total content of these inorganic salts in the bath additives is preferably 5% or more, still preferably 10% or more, by weight.
The organic acids include succinic acid, fumaric acid, malic acid, tartaric acid, citric acid, and benzoic acid. They can be added either individually or as a combination of two or more. A total content of these organic acids in the bath additives is preferably 0.1 to 95% by weight.
The oily components include fats and oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, essential oils, and silicone oils.
The bath additives can further contain other ingredients that are customarily employed in the art. Specific but non-limiting examples of useful ingredients of the bath additives are:
(a) inorganic acids, such as boric acid, metasilicic acid, and silicic anhydride;
(b) crude drugs, such as fennel, chamomillae flos, ginkgo, phellodendron, cinnamon bark, catharmi flos, paeonia radix, ginger, calamus, cnidii rhizoma, angelicae radix, orange peel, Atractylodis Lanceae rhizoma, valerianae radix, bitter orange peel, Japanese mint (Mentha arvensis), hoelen, ginseng radix, and oat, and their extracts;
(c) pigments, such as coal tar dyes of Positive Lists I and II as laid down in Ministry of Health, Labor and Welfare Ordinance No. 30, such as yellow No. 4, blue No. 1 and yellow No. 202(1), and natural pigments permitted as food additives, such as chlorophyll, riboflavin, crocin, safflower, and anthraquinone;
(d) vitamins, such as vitamin A, vitamin C, vitamin d, and vitamin E;
(e) fragrances; and
(f) others, such as sulfur, sinter deposit, mineral sand, mica powder, neutral white clay, roasted rice bran, bactericides, antiseptics, and other ingredients necessary to make preparations.
The bath additive is prepared by adding to the warming composition arbitrary ingredients chosen from the above-described substances according to necessity. The content of these arbitrary ingredients in the composition can range 0 to 99% by weight. The bath additive composition thus prepared may be stabilized or made into an emulsion by addition of an adequate amount of water within a range of from 0.01 to 90% by weight. Similarly to known bath additives, the bath additives can have any form, such as powders, granules, tablets, and liquids.
The present invention will now be illustrated in greater detail with reference to Examples in view of Comparative Examples, but it should be understood that the invention is not limited thereto. Unless otherwise noted, all the percents are by weight.
Abbreviations used hereunder have the following meanings and particulars of commercially available products used hereunder are also as follows.
CA-10: 3-(l-menthoxy)propane-1,2-diol
TPG-1: 3-(l-menthoxy)-2-methylpropane-1,2-diol
TK-5: 3-(1-Methoxy)ethan-1-ol
VBE: Vanillyl butyl ether
Alscope TAP-30: Sodium polyoxyethylene lauryl ether sulfate (3E.O.) (27%), available from Toho Chemical Industry Co., Ltd.
SWANOL AM-101: 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazoliumbetaine (40%), available from Nikko Chemicals Co., Ltd.
Poise C-60H: o-[2-Hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride, available from Kao Corporation
Amizol CDE: Coconut oil fatty acid diethanolamide, available from Kawaken Fine Chemicals Co., Ltd.
BHT: 2,6-Di-t-butyl-4-methylphenyl
Texin SS-1: Disodium polyoxyethylene lauryl sulfosuccinate (1E.O.) (42%), available from Cognis Japan Plantaren 2000upnp: Alkyl (C8-16) glucoside, available from Cognis Japan.